Experiment No.

Oxidation of a Secondary Alcohol: Cyclohexanone from Cyclohexanol

I. Introduction

Oxidation-reduction reactions play an important role in organic chemistry. Oxidation of

alcohols form aldehydes, ketones or carboxylic acids is a fundamental and widely used reaction.
Primary alcohols can be oxidized to aldehydes or carboxylic acids while secondary alcohols
oxidize to ketones. Tertiary alcohols are resistant to oxidation

In this experiment a secondary alcohol is oxidized to form a ketone. The oxidation is

done by a very large number of oxidizing agents, including Sodium dichromate, pyridium
chlorochromate, and Sodium hypochlorite (household bleach). The purpose of this lab is to
synthesize cyclohexanone. Sodium dichromate (Na2Cr2O7) will be used as a source of Chromic
acid (H2CrO4) to oxidize cyclohexanol into cyclohexanone. Since, Chromic acid will be used as
we all know from the previous experiments that Chromic acid is hazardous several precautions
and safety measures must be implemented in conducting the experiment.

We will be synthesizing cyclohexanone but do we know what is it used for? One of the
applications of cyclohexanone is that it is used as a precursor for nylon. This makes it one of
the largest mass produced chemicals in the industry. The transformation of cyclohexanol to
cyclohexanone is a commercially important process. In large chemical plants a catalytic
dehydrogenation process is used instead of Chromic acid.

This process was used to make 1.1 trillion pounds of cyclohexanone in the US in 1995.

Most of the commercial cyclohexanone goes on to make an oxime, then it undergoes a

rearrangement to form caprolactam which is the starting material of Nylon 6.
 Nylon-6 is one of the most widely used nylons in the world. This polymer goes into such
materials as nylon windbreakers, shoe strings, automobile components and automobile tire
cord.

II. Results

Due to the unavailability of materials the experiment was not conducted and thus, no
results were obtained. Still the synthesis of cyclohexanone will be discussed from a theoretical
basis.

III. Discussion

A. Synthesis and Purification of Cyclohexanone

The first part of the experiment is the preparation of chromic acid. Since, chromic acid is
not stable for long periods of time. For a resolution Sodium dichromate is reacted with acetic
acid to produce chromic acid. The conversion of Na2Cr2O7 to H2CrO4 by action of an acid is
shown by the following equation:

H2O
Na2Cr2O7 + 2H+ [H2Cr2O7] 2 H2CrO4 + 2Na+

Once the chromic acid was prepared combine it to the cooled and acidified cyclohexanol
and allow the reaction to proceed given by the instructions in the manual. This part is where
the oxidation is happening.
 As for the oxidation the chromic acid complexes with the oxygen on the hydroxyl group
of the cyclohexanol. At the same time the oxygen on the hydroxyl group of the chromic acid is
being protonated by the acetic acid present in the solution.

Eventually the Cr to the protonated oxygen bond will cleave off as water which is a good
leaving group. A diagram showing that portion of the mechanism is given below:

The following step is the deprotonation of the positive charge on the oxygen adjacent to
the cyclic ring by the acetate ions that was generated from the previous steps. This then results
to the formation of a chromate ester.
 The final steps of this mechanism are the removal of the chromate ester from the
complexed cyclohexanol and the oxidation of the carbinol carbon. The former is achieved by
deprotonating the carbinol carbon with water. This is achieved by deprotonating the carbinol
group with water. After the hydrogen was abstracted a double bond between the carbon and
oxygen is formed then finally the chromate ester will be removed. The final product
cyclohexanone was now produced.

The product can be separated from the reaction mixture by distillation. Distill the
mixture until no more oil passes over with water. Cyclohexanone has some solubility in water to
decrease its solubility enough amounts of sodium chloride was added. This was done to salt out
the cyclohexanone from the aqueous phase, just as we did in the cyclohexene experiment. The
idea is to saturate the aqueous layer with the very polar sodium chloride to drive the
cyclohexanone away from the water layer. Stir the mixture until most of NaCl dissolves. You
will see a narrow clear organic layer on top of a cloudy aqueous solution. Let the solution sit
and separate for a few minutes. The aqueous layer is on the bottom and the cyclohexanone
organic layer is on the top. Drain off the bottom layer into a small beaker and save the
cyclohexanone. Then, extract the aqueous layer with ether to remove any water that was left
behind.

Cyclohexanone is generally slightly soluble in water, but it is more in ether. The ether to
be used is insoluble in water and will form a separate layer. The main purpose of the ether will
be to dissolve the organic material (the cyclohexanone) in the process pushing off the water
molecules toward the aqueous layer. The ether extracts was then combined and dried with
anhydrous Na2SO4 the purpose of adding a drying agent is to remove excess water in the
reaction mixture and in order to have a maximum purity of the product. Then the product was
added was with potassium carbonate (K2CO3) to neutralize all of the acetic acid that distilled
over with your product. You should see evolution of CO2 gas. Keep adding the solid until there
is no more bubbling and test with litmus to see that it is neutral.

The reaction equation for this neutralization is shown below:

K2CO3 (aq)+ 2CH3COOH (aq) 2CH3COOK (aq) + H2O (l) + CO2 (g)
The final distillation step follows for the collection of the final product of cyclohexanone. Collect
the cyclohexanone at around 152-155°C. The collected cyclohexanone can then be weighed
and was tested.

B. Possible Side reactions

1. Formation of Dicyclohexyl ether

H -H2O
H+
+
OH O +
H
Cyclohexanol

+ HO
O
Dicyclohexyl ether

This side reaction can be minimized by the drop wise addition of cyclohexanol with
gentle swirling after every drop and by controlling the reaction temperature.

2. Formation of Cyclohexene

H -H2O
H+
+
OH O +
H
Cyclohexanol
H

-H+
+

Cyclohexene

The same technique is also used to minimize this side reaction.

C. Comparison of Product and Starting Material

The product and starting material were compared using the following tests:

 Test with Sodium (Na) metal

If a small piece of sodium is dropped into some alcohol, it reacts steadily to give off
bubbles of hydrogen gas and leaves a colourless solution of sodium alkoxide. The formation of
hydrogen bubbles indicates a positive test. If you react Na metal with cyclohexanol it is
expected that the reaction would release bubbles. The formula for this reaction is shown below:

2Na (s) + 2C6H11OH (aq) 2C6H11ONa (aq) + H2 (g)

Under normal conditions, sodium metal does not react with ketones. So this means that
when the tested solution produces hydrogen gas it is cyclohexanol and if it doesn’t it is
cyclohexanone.

 Test with Dilute Potassium permanganate (KMnO4)

The test with dilute potassium permanganate is to differentiate the oxidizability between
cyclohexanone and cyclohexanol. The cyclohexanone tends to be oxidized by the potassium
permanganate into cyclohexanone as shown in the following equation:

Whereas, ketones does not contain hydrogen that is primarily required for oxidation.
Thus, ketones will give a negative result for this test. So basically there will be a color change
from purple to brown with the cyclohexanol and no change in color with the cyclohexanone.
D. Derivatization of Cyclohexanone

The compound 2,4-dinitrohydrazine is usually used to identify the presence of a carbonyl

group in a molecule. In this part the cyclohexanone is reacted with 2, 4-dinitrohydrazine which
reacts with the carbonyl group of a compound to form a hydrazone. In the case of
cyclohexanone, the ending product is known as cyclohexanone 2, 4-dinitrophenyl hydrazone
which is essentially a derivative of cyclohexanone. The presence of a thick yellow or orange
precipitate confirms the presence of a carbonyl in a ketone or aldehyde group

The mechanism of its formation is worth considering. The first step is a typical addition
to a C=0 bond. The resulting intermediate, with OH and NH groups on the same carbon, is
unstable and loses H 2O to form the C=N compound. The mechanism is shown below:
 The obtained product will be recrystallized and subjected to melting point determination
to determine its identity. If the product has a close melting point value to the literature value of
the cyclohexanone derivative which is in the range of 159-160°C then the initial molecule was
indeed the cyclohexanone if otherwise, it is something else.

IV. Conclusion

Therefore, oxidation of alcohols is a fundamental and widely used reaction and forming
aldehydes, ketones or carboxylic acids. Primary alcohols can be oxidized with the use of
oxidizing agents to aldehydes or carboxylic acids while secondary alcohols oxidize to ketones.
Tertiary alcohols however are resistant to oxidation. Generally oxidation reactions as defined in
organic chemistry involves the addition of oxygen or the removal of hydrogen. In this
experiment the cyclohexanol, a secondary alcohol was oxidized into a secondary ketone,
cyclohexanone. The success of the oxidation can be verified by testing the obtained product by
the addition of a sodium metal, dilute potassium permanganate and with 2, 4-dinitrohydrazine
(the details of these test were mentioned in the discussion. If the product gave a positive result
among these tests then it is evident that the obtained compound was indeed the
cyclohexanone.

V. Answers to Questions

1. Give the general theoretical definition of oxidation and reduction in terms of

electron transfer. Why are these definitions sometimes difficult to apply in
organic chemistry?

With respect to electron transfer, oxidation is essentially the loss of electrons and
reduction is the gaining of electrons. While these definitions applies well in inorganic
chemistry with the concepts of ionic and free radical reactions, the application is sometimes
harder in the field of organic chemistry because of the fact that it makes more sense to look
at organic oxidation and reduction reactions in terms of carbon connections and carbon
oxidation states instead of electron transfer routes.

2. Redefine the terms oxidation and reduction as used in organic chemistry. Is

cyclohexanol oxidized or reduced when it is converted into cyclohexanone?

In reference to organic chemistry, oxidation is a process by which a carbon atom gains

bonds to more electronegative atoms like oxygen and a reduction is a process by which a
carbon atoms gains bonds to less electronegative atoms like hydrogen. Using this definition
for oxidation and reduction, we see that the carbon in question gains bonds to a more
electronegative atom, the oxygen. This results in an increase in the oxidation number of
 that particular carbon and this increase indicates that the cyclohexanol is oxidized in this
reaction. An illustration of this is shown below:

3. The most important side reaction which complicates the oxidation of a primary
alcohol to an aldehyde is the ready oxidation of aldehydes to carboxylic acids by
chromic acid. This further, undesired, oxidation can be minimized by a) adding
the chromic acid to the primary alcohol rather than the reverse and b) by
distilling the aldehyde from the reaction mixture as it is formed. Explain why the
above measures can minimize the further oxidation of aldehydes to carboxylic
acids.

As is shown in the question, the full oxidation of the primary alcohol into carboxylic acids
can be halted at the aldehyde step in two ways. The first is by adding the chromic acid to
an excess of the primary alcohol. The excess of the alcohol essentially makes sure that
there isn’t any of the oxidizing agent left over to carry out the second stage of the oxidation
into the carboxylic acid. And the second method is to remove the aldehyde from the mixture
as soon as it is formed which removes the aldehyde from the reaction vessel and prevents
any further oxidation from taking place.

4. Ketones are stable toward oxidizing agents in neutral or mildly acidic media.
However, under alkaline or strongly acidic conditions enolizable ketones will
undergo oxidation with cleavage to give two carbonyl fragments. For example,
cyclohexanone can be converted to adipic acid by treatment with alkaline
KMnO4.

a. Write the structure for the enol tautomer of cyclohexanone.

b. Why is cyclohexanone oxidized by alkaline or strongly acidic KMnO4 but not
neutral KMnO4?

This refers to the effectiveness of potassium permanganate as an oxidizing agent

based on the conditions. The most effective medium would be a strongly acidic because
the permanganate is reduced to the greatest extent in the medium. Same goes
somewhat for alkaline conditions. The cyclohexanone will not be oxidized in a neutral
solution because at neutral pH, the permanganate is least effective as an oxidizing
agent.

c. Write the balanced equation for the oxidation of cyclohexanone to adipic acid
by using alkaline KMnO4.

2HCl + C6H10O + 2KMnO4 HOOC(CH2)4 COOH + 2MnO2 + 2KCl + H2O